Silicon particle, silicon particle superlattice and method for producing the same

ABSTRACT

A production method, comprising a step of synthesizing silicon particle-containing silicon oxide particles by performing a gas phase reaction of monosilane gas and oxidizing gas for oxidizing the monosilane gas and a step of removing the silicon oxide with hydrofluoric acid after holding the silicon oxide particle powder in an inert atmosphere at 800-1400° C., provides high-purity silicon nanoparticles which are highly practical as material powder for high-performance light-emitting elements and electronic parts in an industrial scale.

CROSS-REFERENCE

This application is a Divisional of co-pending application Ser. No.10/592,864 filed on Sep. 13, 2007 and for which priority is claimedunder 35 U.S.C. §120. Application Ser. No. 10/592,864 is the nationalphase of PCT International Application No. PCT/JP2005/002574 filed onFeb. 18, 2005 under 35 U.S.C. §371. The entire contents of each of theabove-identified applications are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to nanometer (nm)-sized high-puritysilicon particles and a method for producing the same.

The present invention also relates to a silicon particle superlatticewhich has nanometer (nm)-sized silicon particles two-dimensionally orthree-dimensionally arranged periodically with regularity and a methodfor producing the same.

BACKGROUND ART

Silicon particles (silicon nanoparticles) having a particle diameter ofthe order of nanometers have physical and chemical propertiesconsiderably different from those of bulk silicon, and are attracting alot of attention as new functional material in recent years. Forexample, the silicon nanoparticles have a band structure different fromthat of the bulk silicon based on the quantum confinement effects andsurface level effect, and a luminous phenomenon which is not observed onthe bulk silicon is observed, so that it is expected to be applied asmaterial for a novel silicon light emitting device.

Ordinary fine silicon powder obtained by finely pulverizing silicon hasphysical and chemical properties substantially corresponding with thoseof the bulk silicon. Meanwhile, the silicon nanoparticles have a veryfine particle diameter, a relatively small particle size distributionwidth, and high purity. Therefore, it is considered that a peculiarproperty such as a luminous phenomenon quite different from the bulksilicon is expressed.

Conventionally, as the method for production of silicon nanoparticles,there have been used, for example, (1) a method of passing siliconvaporized by a first high-temperature plasma generated between mutuallyopposed silicon electrodes through a second high-temperature plasmagenerated by electrodeless discharge in a reduced-pressure atmosphere(Patent Literature 1), (2) a method of separating and removing siliconnanoparticles from a positive electrode, which is formed of a siliconwafer, by electrochemical etching (Patent Literature 2), and (3) amethod for electrode reduction of a halogen-containing organic siliconcompounds using reactive electrodes (Patent Literature 3).

But, the above-described methods (1), (2) are hard to improveproductivity because they have a considerably low silicon nanoparticlegeneration speed. The above-described method (3) has a halogen elementsuch as Cl in raw material, and it is easily mixed into a product, sothat a total amount of Na, Fe, Al, Cl is hard to become 10 ppm or less.

Therefore, it is quite difficult to produce high-purity siliconnanoparticles which are useful as material powder for high-performancelight-emitting elements and electronic parts in an industrial scale.

Meanwhile, for expression of a luminous phenomenon or the like based onthe above-described band structure and surface level effect, a so-calledsuperlattice structure that has silicon particles having a uniformparticle diameter of the order of nanometers two-dimensionally orthree-dimensionally arranged periodically with regularity must beformed.

Therefore, as a specific method of using the silicon particles of theorder of nanometers as new functional material, there is required amethod that selectively removes particles having a particular size fromsilicon particles produced in a large amount and arranges themtwo-dimensionally or three-dimensionally, or forms a superlattice.

Conventionally, as a method for production of silicon particles or asuperlattice containing the silicon particles, or a film or a formedproduct having the silicon particles arranged, there are proposed (a)chemical vapor deposition (CVD) method (Patent Literatures 4, 5), (b)spin coat method (Patent Literature 6), (c) method of straining asuspension containing particles through a porous barrier wall to obtainparticles (Patent Literature 7), (d) method of using particleelectrophoresis (Patent Literature 8), and the like.

But, the above method (a) is often performed in vacuum at a hightemperature or in a plasma atmosphere, so that a highly controlledvacuum heating device or a plasma generating device is necessary and thecost becomes high. And, the method (b) does not need an expensive devicesuch as that used for the method (a) but product yield lowersconsiderably. The methods (c), (d) arrange particles on the porousbarrier wall or electrode, but there is no appropriate method forremoval of a film or formed product which is formed of a superlatticefrom such materials.

The superlattice containing the conventional silicon particles obtainedby the above methods has variations in particle diameter, so that theband structure or the surface level becomes unstable. When it is used asa light-emitting element, luminous efficiency does not become highenough, and when it is used as electronic parts, there is a possibilityof malfunction.

[Patent Literature 1] Japanese Patent Laid-Open Publication No. Hei6-279015

[Patent Literature 2] Japanese Patent Publication No. 2003-515459

[Patent Literature 3] Japanese Patent Laid-Open Publication No.2002-154817

[Patent Literature 4] Japanese Patent Laid-Open Publication No. Hei5-62911

[Patent Literature 5] Japanese Patent Laid-Open Publication No. Hei6-349744

[Patent Literature 6] Japanese Patent Laid-Open Publication No. Hei11-1308867

[Patent Literature 7] Japanese Patent Laid-Open Publication No.2002-279704

[Patent Literature 8] Japanese Patent Laid-Open Publication No.2003-89896

SUMMARY OF THE INVENTION

Accordingly, the present inventors have made a devoted study to find aproduction method capable of producing high-purity silicon nanoparticlesthat can realize high-performance light-emitting elements and electronicparts in an industrial scale. As a result, it was found that high-puritynanometer-sized silicon particles having relatively uniform particlediameters can be produced in an industrial scale by a method of removingexcess silicon oxide with hydrofluoric acid after heating underparticular conditions silicon particle-containing silicon oxide producedby a gas phase method using particular materials. Thus, the presentinvention was completed.

In other words, the silicon particles of the present invention has aparticle diameter of 1-50 nm, and a total amount of Na, Fe, Al, Cl is 10ppm or less.

And, the silicon powder of the present invention contains 90 mass % ormore of silicon particles having a particle diameter of 1-50 nm and atotal amount of Na, Fe, Al, Cl is 10 ppm or less.

Besides, a method for production of silicon particles of the presentinvention comprises synthesizing silicon oxide particles which containsilicon particles by performing a gas phase reaction of monosilane gasand oxidizing gas for oxidizing the monosilane gas, and removing thesilicon oxide by hydrofluoric acid after keeping the silicon oxideparticles in an inert atmosphere at 800-1400° C.

And, the present inventors have made a devoted study to find a method ofefficiently producing a superlattice of silicon particles capable ofrealizing high-performance light-emitting elements and electronic partsat a low cost and completed the present invention.

Specifically, the silicon particle superlattice of the present inventionis a silicon particle superlattice formed of plural silicon particles,wherein the silicon particles have an average particle diameter of 1-50nm, and a variation coefficient of a particle diameter is 20% or less.

The method for production of the silicon particle superlattice of thepresent invention has a step that adds a hydrophobic solvent to thesuspension which has hydrophobic silicon particles dispersed into water,leaves it at rest, and arranges the silicon particles at the interfacebetween an aqueous phase and an organic phase. And, the method includes“the suspension contains hydrofluoric acid” and “the hydrophobic solventis 1-octanol” as desirable modes.

The silicon particle superlattice structure of the present invention hasthe above silicon particle superlattice on the hydrophobic surface ofthe solid substrate having the hydrophobic surface and includes “thesolid substrate must be a silicon substrate or a graphite substrate” asa preferable mode.

Besides, the light-emitting elements and electronic parts of the presentinvention have at least either the above silicon particle superlatticeor the above silicon particle superlattice structure.

EFFECTS OF THE INVENTION

The silicon particles of the present invention are nanoparticles havinga relatively uniform particle diameter of 1-50 nm and a total amount ofNa, Fe, Al, Cl of 10 ppm or less and highly pure.

Generally, silicon particles have a band structure different from bulksilicon according to the quantum confinement effects and surface leveleffect, a particle diameter is determined to be 1-5 nm when a luminousphenomenon which is not observed on bulk silicon is shown, and a quantumwell structure that is important when applied to electronic parts isrecognized for an aggregate of particles having a uniform particlediameter of 10 nm or less. The silicon particles of the presentinvention have a particle diameter of 1-50 nm, including a range ofparticle diameters that a quantum confinement effect, a surface leveleffect or a quantum well structure is expressed.

And, if silicon contains an impurity such as Na, Fe, Al or Cl, animpurity level is formed in the band structure, lowering luminousefficiency of the light-emitting element or causing a malfunction of theelectronic parts. The total amount of Na, Fe, Al, Cl of the siliconparticles of the present invention is 10 ppm or less, so that theimpurity level is not formed, and the above defect does not occur in thelight-emitting element or the electronic parts.

Therefore, the silicon particles of the present invention are differentfrom the conventional silicon nanoparticles and highly practicable asmaterial powder for high-performance light-emitting elements andelectronic parts.

The method for production of the silicon particles according to thepresent invention uses a particular silicon-containing gas (monosilanegas) as raw material, reacts it with oxidizing gas under particularconditions to synthesize silicon particle-containing silicon oxide,heats it under particular conditions, and removes excess silicon oxidewith hydrofluoric acid. Thus, it is different from a conventional methodfor production of silicon nanoparticles, has high productivity and canproduce in an industrial scale. Therefore, the silicon nanoparticles canbe applied to light-emitting elements and electronic parts in anindustrial scale and are very useful industrially.

The silicon particles configuring the superlattice of the presentinvention have a relatively uniform average particle diameter of 1-50nm, and the variation coefficient of the particle diameter is 20% orless. The superlattice is a lattice-like aggregate of particles that hasparticles of assembled atoms and molecules further assembled mutuallyand two-dimensionally or three-dimensionally arranged periodically withregularity. The superlattice of the present invention having smallvariations in particle diameter can arrange particles having smallvariations in surface level at a remarkable periodicity, so thatmaterial having a desired band structure can be produced stably.

Thus, the silicon particle superlattice can produce various types ofband structures in accordance with the intended use, when used as alight-emitting element, a sufficient luminous efficiency can beobtained, and when used as an electronic part, material which seldomcauses malfunction can be produced. Therefore, the performanceimprovement of the electronic instruments becomes easy, and the presentinvention highly contributes to functional material productiontechnology in an industrial scale and is very useful industrially.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 TEM photograph showing an example of a silicon particlesuperlattice according to the present invention.

FIG. 2 Fourier transform image showing an example of a silicon particlesuperlattice according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Silicon Particles

Silicon particles of the present invention have a particle diameter of1-50 nm, and preferably 1-30 nm. If the particle diameter is not in theabove ranges, the quantum confinement effects, surface level effect orquantum well structure suitable for application to light-emittingelements and electronic parts cannot be expressed. And, a total amountof Na, Fe, Al, Cl of the silicon particles of the present invention is10 ppm or less, and preferably 5 ppm or less. If the total amount of Na,Fe, Al, Cl exceeds 10 ppm, the properties of light-emitting elements andelectronic parts are affected by impurities.

<Silicon Powder>

Silicon powder of the present invention contains 90 mass % or more ofsilicon particles of the present invention. If a content of siliconparticles of the present invention is 90 mass % or more, unnecessaryparticles can be removed directly or by a simple post-treatment, but ifit is less than 90 mass %, the easy removal of unnecessary particles islost.

<Method for Production of Silicon Particles>

Silicon particles of the present invention can be produced by, forexample, heating silicon particle-containing silicon oxide particlessynthesized from a gas phase using monosilane gas and an oxidizing gasin a prescribed atmosphere at a prescribed temperature, and removingsilicon oxide.

Specifically, monosilane gas is first reacted with oxidizing gas in agas phase to synthesize silicon particle-containing silicon oxideparticles. The reaction is performed by introducing monosilane gas andoxidizing gas into a reaction vessel.

Here, material for a silicon source of the present invention ismonosilane gas. In addition to the monosilane gas, whensilicon-containing gas, e.g., chlorosilanes (SiH_(n)Cl_(4-n), n=integerof 0 to 3) is used as material, a total amount of Na, Fe, Al, Cl exceeds10 ppm.

The oxidizing gas is not particularly limited if it could oxidize themonosilane gas, and oxygen gas, air, steam, nitrogen dioxide, carbondioxide and the like can be used, and oxygen gas is particularlydesirable in view of ease of handling, ease of reaction control and thelike. In order to facilitate the reaction control, a third gas such ashydrogen, nitrogen, ammonia, carbon monoxide or the like can also beintroduced into the reaction vessel as long as it does not disturb thereaction in addition to the inert gas such as argon, helium, to dilutethe monosilane gas and the oxidizing gas.

The reaction is preferably performed with the reaction vessel kept at atemperature of 500° C. to 1000° C. and a pressure of 10-1000 kPa. Thereaction vessel generally used is made of a high-purity material such asquartz glass, and its shape is not particularly limited but desired tohave a tube shape. The axial direction of the tube may be eithervertical or horizontal. For the method of heating the reaction vessel,any method such as resistance heating, high-frequency induction heating,infrared radiation heating or the like can be used.

The silicon particle-containing silicon oxide particles produced in thereaction vessel are exhausted together with a gas flow from the systemand recovered from a powder collecting apparatus such as a bag filter.

The recovered silicon oxide particles are then held in an inertatmosphere at 800 to 1400° C. Thus, the silicon particles contained inthe silicon oxide particles are adjusted to a particle diameter of 1 to50 nm. If the holding temperature is less than 800° C., the siliconparticles have a particle diameter of less than one nm, the impuritiesare likely to remain in the silicon, and the total amount of Na, Fe, Al,Cl exceeds 10 ppm. If the temperature exceeds 1400° C., the siliconparticles have a particle diameter of exceeding 50 nm.

The inert atmosphere gas used can be hydrogen, nitrogen, ammonia, andcarbon monoxide other than the inert gas such as argon and helium, butargon gas is particularly desirable in view of ease of handling and thelike.

After the particle diameter of the contained silicon particles isadjusted, the silicon oxide particles are added to and dispersed intowater. The particles are dispersed by ultrasonic waves or a stirrer, butit is particularly desirable to use ultrasonic waves. After the siliconoxide particles are dispersed into water to suspend, hydrofluoric acidis added to the suspension. The silicon particles contained in thesilicon oxide particles are not dissolved by hydrofluoric acid, but thesurrounding silicon oxide is dissolved and removed, so that only thesilicon remains and the silicon particles of the present invention canbe obtained.

<Silicon Particle Superlattice>

Silicon particles configuring the silicon particle superlattice of thepresent invention have an average particle diameter of 1-50 nm, andpreferably 5-20 nm. If the average particle diameter is less than onenm, it is hard to arrange the particles with regularity. And, if theaverage particle diameter exceeds 50 nm, the physical and chemicalproperties become hardly different from those of the bulk silicon, andmeaning of forming the superlattice is lost.

The particle diameter of the silicon particles have variationcoefficient of 20% or less. If the variation coefficient of the particlediameter exceeds 20%, variations in particle diameter are so large thata band cannot be formed. According to the present invention, “thevariation coefficient of the particle diameter” is a value obtained bydividing a standard deviation of the particle diameter by an averagevalue, which is an index indicating variations in particle diameter,indicating that the smaller the value, the smaller the variations inparticle diameter.

As a specific method of measuring the average particle diameter and thevariation coefficient, there is, for example, a method of performingimage analysis of a transmission electron microscope (TEM) image of asuperlattice. To analyze the superlattice formed of a large number ofsilicon particles, it is desirable to perform on 100 or more particles.

It is possible to judge with reference to the TEM image whether or not alot of particles are mutually arranged with regularity in the siliconparticle superlattice of the present invention, but for more detail,judgment can be made on a Fourier transform image of the TEM image.Where particles are mutually arranged with regularity, a subject spotcorresponding to the formation of the lattice appears on the Fouriertransform image. For example, FIG. 1 is the TEM image as one example ofthe silicon particle superlattice of the present invention, and FIG. 2is its Fourier transform image. In FIG. 2, spots having 6 times of beingan object are observed on the Fourier transform image, and it is seenthat a superlattice with the particles mutually arranged with regularityis formed.

<Silicon Particle Superlattice Production Method, Silicon ParticleSuperlattice Structure, Light-Emitting Element, Electronic Parts>

Then, a method for production of a silicon particle superlattice of thepresent invention will be described.

First, a method for production of a lot of silicon particles is notparticularly limited if the obtained silicon particles havehydrophobicity. For example, there can be applied a method of subjectingmonosilane gas and oxidizing gas for oxidizing the monosilane gas to agas phase reaction to synthesize silicon particle-containing siliconoxide particles and holding the particles in an inert atmosphere at800-1400° C. This method is preferable because silicon particles whichare contained in the silicon oxide are adjusted to a particle diameterof about 1-50 nm by keeping under heat in the inert atmosphere. Asdescribed later, variations in particle diameter are decreased in a stepof arranging the silicon particles on the interface between the aqueousphase and the hydrophobic solvent, so that it does not matter even ifvariations at this time is relatively large.

Silicon oxide of the silicon particle-containing silicon oxide particlescan be removed by hydrofluoric acid. This method is particularlyconvenient because it is a step of exposing the silicon particlescontained in the silicon oxide and also serves as a step of givinghydrophobicity to the surfaces of the silicon particles. The reason whythe hydrophobicity is given to the surfaces of the silicon particles bythe hydrofluoric acid is considered that the silicon oxide which isaround the silicon particles is removed by the hydrofluoric acid, andhydrogen fluoride (HF) acts on the uppermost surface of the exposedsilicon particles at the same time to bond silicon atoms and hydrogen,and the particle surface is modified with hydrogen atoms.

At this time, where the silicon oxide particles are previously dispersedinto water to prepare a suspension and the hydrofluoric acid is drippedto the suspension, the silicon particles having hydrophobicity can beobtained in a state of the suspension. Therefore, the method forproduction of the silicon particle superlattice of the present inventioncan be applied as it is. Thus, it is preferable. And, to improvedispersibility of the silicon particles, it is desirable to applyvibration of ultrasonic waves to the suspension.

Then, a hydrophobic solvent is added to the suspension. Thus, thehydrophobic silicon particles are moved from the aqueous phase into theorganic phase (hydrophobic solvent). At this time, to accelerate themovement of the particles, it is desirable to continue the applicationof vibration of ultrasonic waves after the addition of the hydrophobicsolvent. If the silicon particles do not have hydrophobicity, themovement into the hydrophobic solvent does not take place.

Then, it is left at rest to separate the aqueous phase and the organicphase, and the silicon particles dispersed into the hydrophobic solventare gradually aggregated and arranged on the interface between theaqueous phase and the organic phase. At the time of the aggregation andarrangement, a superlattice of the silicon particles is formed on theinterface between the aqueous phase and the organic phase because theparticles having similar particle diameters are selectively aggregatedand arranged though the reason is not known. First, in a case wherepowder of silicon particles having relatively large variations inparticle diameter is used, a lot of superlattices having differentaverage particle diameters are formed at different portions of theinterface. If the solvent is not hydrophobic, the interface is notformed between the aqueous phase and the organic phase, so that thesuperlattice is not formed.

Specific examples of the hydrophobic solvent include an aliphatichydrocarbon-based solvent such as water-insoluble or poorlywater-insoluble n-hexane or n-heptane, an alicyclic hydrocarbon-basedsolvent such as cyclohexane or methylcyclohexane, an aromatichydrocarbon-based solvent such as toluene or xylene, higher fattyalcohols such as 1-butanol, 1-octanol, and the like. Among them,1-octanol having an appropriate viscosity is particularly desirable toperform smooth aggregation and arrangement of the silicon particles onthe interface between the aqueous phase and the organic phase.

The time period for application of ultrasonic vibration after theaddition of the hydrophobic solvent and the time period of leaving atrest are not limited especially, but where the hydrophobic solvent is1-octanol, it is desirable that the ultrasonic vibration after theaddition is performed for about 30 minutes to one hour, and then thetime period of leaving at rest is two days or more.

Thus, the superlattice formed of the silicon particles which are formedon the interface between the aqueous phase and the organic phase ismoved onto a solid substrate having a hydrophobic surface after beingseparated by means of a semipermeable membrane, for example, a collodionmembrane. Thus, a superlattice structure directly formed on thesubstrate can be obtained. Examples of the solid substrate having thehydrophobic surface include a silicon substrate (silicon wafer), agraphite substrate and the like.

It is also possible to directly form the superlattice on the substratehaving the hydrophobic surface by adding the hydrophobic solvent toseparate the aqueous phase and the organic phase, inserting the solidsubstrate having the hydrophobic surface immediately to the position ofthe interface between them so that the hydrophobic surface is directedto the hydrophobic solvent, and then leaving to stand at rest. At thistime, when a hydrophobic region and a hydrophilic region are previouslypatterned on the substrate surface by a lithography technology or thelike, the superlattice can be formed at a desired position of thesubstrate. Especially, where the superlattice structure of the presentinvention is directly formed on the silicon substrate, it becomespossible to use as an element for functional materials such as novellight-emitting elements, electronic parts and the like.

EXAMPLES

The present invention will be further described with reference toExamples and Comparative Examples.

Example 1

Monosilane gas of 0.16 L/min, oxygen gas of 0.4 L/min and dilutingnitrogen gas of 17.5 L/min were introduced into a reaction vessel formedof a quartz glass reaction tube (inside diameter of 50 mm, length of1000 mm) held at a temperature of 700° C. and a pressure of 90 kPa toproduce dark brown powder. It was collected by a metallic filler whichwas disposed downstream of the reaction tube.

The collected powder had a specific surface area of 55 m²/g whenmeasured according to a BET one-point method. The powder was found bychemical analysis to have primary components of silicon (Si) and oxygen(O). And, a bonded state of Si was determined by Si_(2 p) spectrum ofXPS (X-ray photoelectron spectroscopy). There were recognized a peakattributed to Si—Si bonding other than a peak attributed to Si—Obonding, and it was found that silicon particles were contained in theproduced silicon oxide particles.

The powder in 20 g was held at a temperature of 1100° C. for one hour inan argon atmosphere and then cooled to room temperature. One liter ofdistilled water was added thereto, ultrasonic waves were applied for onehour to disperse the powder, thereby producing a suspension. 0.1 literof 5% concentration-hydrofluoric acid (HF) was added to the suspension,and ultrasonic waves were applied for 30 minutes to dissolve and removesilicon oxide. Then, a membrane filter was used to filtrate and wash thesuspension to separate a product, which was then dried to obtain siliconpowder.

It was checked by chemical analysis that the primary component of thepowder was Si, and a total amount of Na, Fe, Al, Cl was 5 ppm. Besides,particles contained in the powder were measured by a transmissionelectron microscope (TEM) to have a particle diameter of 10-40 nm.

Example 2

Monosilane gas at 0.08 L/min, oxygen gas at 0.044 L/min and dilutingargon gas at 18 L/min were introduced into the same reaction vesselformed of the quartz glass reaction tube as that in Example 1 held at atemperature of 750° C. and a pressure of 50 kPa to produce dark brownpowder. It was collected by the same manner as in Example 1.

The collected powder had a specific surface area of 150 m²/g when it wasmeasured. The powder was found by chemical analysis to have primarycomponents of Si and oxygen. Si_(2 p) spectrum of XPS was checked tofind a peek attributed to Si—Si bonding, and it was checked that theproduct was silicon particle-containing silicon oxide particles.

The procedure of Example 1 was performed to obtain silicon powder exceptthat the powder in 20 g was held at a temperature of 900° C. for onehour in a helium atmosphere. It was checked by chemical analysis thatthe primary component of the powder was Si, and a total amount of Na,Fe, Al, Cl was 8 ppm. Besides, particles contained in the powder weremeasured by the TEM to have a particle diameter of 2-24 nm.

Comparative Example 1

The procedure of Example 1 was performed to obtain silicon powder exceptthat 20 g of powder formed of Si-containing silicon oxide particles washeld at a temperature of 1450° C. for one hour in an argon atmosphere.

It was checked by chemical analysis that the primary component of thepowder was Si, and a total amount of Na, Fe, Al, Cl was 4 ppm. Besides,the particles were measured by the TEM for a particle diameter to findthat they were powder formed of particles having a particle diameter of35 nm or more containing 12 mass % of particles having a particlediameter of exceeding 50 nm.

Comparative Example 2

The procedure of Example 1 was performed to obtain silicon powder exceptthat 20 g of powder formed of Si-containing silicon oxide particles washeld at a temperature of 700° C. for one hour in an argon atmosphere.

It was checked by chemical analysis that the primary component of thepowder was Si, and a total amount of Na, Fe, Al, Cl was 18 ppm. Besides,the particles were measured by the TEM for a particle diameter to findthat they were powder formed of particles having a particle diameter of10 nm or less containing 16 mass % of particles having a particlediameter of less than 1 nm.

Comparative Example 3

The procedure of Example 2 was performed to obtain silicon powder exceptthat 20 g of powder formed of Si-containing silicon oxide particles washeld at a temperature of 700° C. for one hour in a helium atmosphere.

It was checked by chemical analysis that the primary component of thepowder was Si, and a total amount of Na, Fe, Al, Cl was 23 ppm. Besides,the particles were measured by the TEM for a particle diameter to findthat they were powder formed of particles having a particle diameter of6 nm or less containing 40 mass % of particles having a particlediameter of less than 1 nm.

Comparative Example 4

The procedure of Example 1 was performed to introduce gas into thereaction vessel to produce dark brown powder except that silicontetrachloride (SiCl₄) gas, which was often used as raw material forpolycrystalline silicon, was used instead of monosilane gas, and thepowder was collected by the same manner as in Example 1.

The collected powder had a specific surface area of 45 m²/g when it wasmeasured. The powder was found by chemical analysis to have primarycomponents of Si and oxygen. Si_(2 p) spectrum of XPS was checked tofind a peek attributed to Si—Si bonding, and it was checked that theproduct was silicon particle-containing silicon oxide powder particles.

The powder in 20 g was used to obtain silicon powder by performing theprocedure of Example 1. The primary component of the powder was Si, andthe particles measured by the TEM had a particle diameter of 5-35 nm.Particularly, chlorine (Cl) was contained in a large amount, and a totalamount of Na, Fe, Al, Cl was 50 ppm.

Example 3

Monosilane gas of 0.16 L/min, oxygen gas of 0.4 L/min and dilutingnitrogen gas of 17.5 L/min were introduced into a reaction vessel formedof a quartz glass reaction tube (inside diameter of 50 mm, length of1000 mm) held at a temperature of 780° C. and a pressure of 90 kPa toproduce dark brown powder. It was collected by a metallic filler whichwas disposed downstream of the reaction tube.

The collected powder had a specific surface area of 62 m²/g whenmeasured according to the BET one-point method. The powder was found bychemical analysis to have primary components of silicon (Si) and oxygen(O). And, a bonded state of Si was determined by Si_(2 p) spectrum ofXPS (X-ray photoelectron spectroscopy). There were recognized a peakattributed to Si—Si bonding other than a peak attributed to Si—Obonding, and it was found that silicon particles were contained in theproduced silicon oxide powder particles.

The powder in 2 g was held at a temperature of 1200° C. for 30 minutesin an argon atmosphere and then cooled to room temperature. 0.1 liter ofdistilled water was added thereto, and ultrasonic waves were applied forone hour to disperse the powder, thereby producing a suspension. 0.01liter of 5% concentration-hydrofluoric acid (HF) was added to thesuspension, and ultrasonic waves were applied for 30 minutes to dissolveand remove silicon oxide. Then, 0.2 litter of 1-octanol was added as ahydrophobic solvent, ultrasonic waves were applied for 30 minutes, andthen the resultant product was left standing for two days.

Then, a support having a collodion membrane adhered to a mesh (#1000)for preparing samples for the transmission electron microscope (TEM) wasused to take a portion around the interface between 1-octanol and anaqueous solution, and the obtained sample was dried at 60° C. for threedays.

The sample observed by the TEM had a structure that the particles shownin FIG. 1 were arranged with regularity. Besides, a Fourier transformimage was pictured in the same field of view to find spots having 6times of being an object shown in FIG. 2, and the formation of asuperlattice was checked. And, for the TEM image of FIG. 1, an image of115 silicon particles was sampled to perform image analysis usingcomputer software (a product of Lasertec Corporation, SALT Ver. 3.62).It was found that an average particle diameter was 9 nm, and theparticle diameter had a variation coefficient of 17%.

Example 4

The procedure of Example 3 was performed to collect dark brown powderexcept that a temperature was changed to 700° C. The powder had aspecific surface area of 42 m²/g. The powder was found by chemicalanalysis to have primary components of silicon (Si) and oxygen (O).There were recognized a peak attributed to Si—Si bonding other than apeak attributed to Si—O bonding by XPS, and it was found that siliconparticles were contained in the produced silicon oxide powder particles.

The procedure of Example 3 was performed except that the powder in 2 gwas held at a temperature of 1100° C. for 60 minutes in an argonatmosphere to dissolve and remove silicon oxide. Then, 0.2 litter ofxylene was added as a hydrophobic solvent, ultrasonic waves were appliedfor 30 minutes, and then the resultant product was left standing for oneday.

Then, the procedure of Example 3 was performed to prepare a TEM sampleexcept that one day drying was performed. In the TEM image, a structurethat particles are arranged with regularity was found there were spotshaving 6 times of being an object on a Fourier transform image, therebychecking the formation of a superlattice. And, for the TEM image, animage of 122 silicon particles was sampled to perform image analysis inthe same manner as in Example 3. It was found that an average particlediameter was 11 nm, and the particle diameter had a variationcoefficient of 15%.

Example 5

0.2 g of silicon particles having a particle diameter of 1-30 nm wereproduced by a laser ablation method that emits high-power laser to asilicon wafer in vacuum. The particles were added to 10 ml of distilledwater, and ultrasonic waves were applied for one hour to disperse thepowder to prepare a suspension. 0.01 liter of 5%concentration-hydrofluoric acid (HF) was added to the suspension, andultrasonic waves were applied for one hour. Then, 20 milliliter of1-octanol was added as a hydrophobic solvent, ultrasonic waves wereapplied for 30 minutes, and then the resultant product was left standingfor two days.

Then, the procedure of Example 3 was performed to prepare a TEM sample.In the TEM image, a structure that particles are arranged withregularity was found there were spots having 6 times of being an objecton a Fourier transform image, thereby checking the formation of asuperlattice. And, for the TEM image, an image of 147 silicon particleswas sampled to perform image analysis in the same manner as in Example3. It was found that an average particle diameter was 7 nm, and theparticle diameter had a variation coefficient of 17%.

Example 6

2 g of powder formed of silicon particle-containing silicon oxideparticles synthesized in the same manner as in Example 3 was held at atemperature of 1100° C. for one hour in an argon atmosphere, siliconoxide was dissolved and removed in the same manner as in Example 3, 0.2litter of 1-octanol was added as a hydrophobic solvent, and ultrasonicwaves were applied for 30 minutes.

Then, the application of the ultrasonic waves was stopped, and when theaqueous solution and the hydrophobic solvent had a phase separation toform an interface, and a natural oxidized film was immediately removedby dipping in a 2%-hydrofluoric acid solution for 30 minutes. Besides, asilicon wafer having a hydrophobitized (111) plane exposed on thesurface by dipping in a solution of ammonium fluoride (NH₄F) adjusted topH 8 for 10 minutes was horizontally inserted in the vicinity of theinterface between the aqueous solution and the hydrophobic solvent suchthat the surface undergone the hydrophobitization was directed to thehydrophobic solvent (namely, upward), and left standing for two days.

After leaving at rest, the silicon wafer was dried, and thehydrophobitized surface was observed under a field emission scanningelectron microscope (FE-SEM). A structure that the particles werearranged on the plane with regularity was observed, and it was foundthat a superlattice of the silicon particles was formed. An image of 105silicon particles obtained by the FE-SEM image was sampled to performimage analysis. It was found that an average particle diameter was 5 nm,and the particle diameter had a variation coefficient of 18%.

Ultraviolet ray was emitted to the silicon wafer having the siliconparticles arranged, and orange light emission was checked.

Comparative Example 5

Silicon particles were directly deposited on the surface of the siliconwafer hydrophobitized in the same manner as in Example 6 by the laserablation method to form a film of silicon particles. The film surfacewas observed by the FE-SEM to observe a structure that particles werepartly arranged on the surface with regularity, and it was found that asuperlattice of silicon particles was formed. An image of 167 siliconparticles obtained by the FE-SEM image was sampled to perform imageanalysis at a portion where the superlattice was formed. It was foundthat an average particle diameter was 5 nm, and the particle diameterhad a variation coefficient of 29%.

Ultraviolet ray was emitted to the portion of the silicon wafer havingthe silicon particles arranged, and no light emission was observed.

Comparative Example 6

In Example 3, when the aqueous solution and 1-octanol were separatedwithout leaving to stand at rest for two days after the addition of1-octanol, the silicon particles dispersed in the 1-octanol wereimmediately taken with a dropper, dripped on the same support as that inExample 3 and dried at 60° C. for three days. The sample was observed bythe TEM to find that a structure of particles arranged or a spot on aFourier transform image were not recognized and that a superlattice wasnot formed.

Comparative Example 7

The procedure of Example 5 was performed to produce a suspension ofsilicon particles. 0.2 liter of xylene was added thereto without addinghydrofluoric acid, ultrasonic waves were applied for 30 minutes, andthen the resultant product was left standing for one day. It was foundthat the silicon particles did not move into the xylene and did not havehydrophobicity.

The suspension was taken with a dropper, dripped on the same support asthat in Example 3 and dried at 60° C. for three days. The sample wasobserved by the TEM to find that a structure of particles arranged or aspot on a Fourier transform image were not recognized though the siliconparticles were observed and that a superlattice was not formed.

INDUSTRIAL APPLICABILITY

According to the present invention, a large amount of powder ofnanometer-sized silicon particles can be synthesize at a highproductivity in an industrial scale, without requiring a specialelectrolytic apparatus or plasma generating device, and the obtainedpowder can be used as material powder to contribute to practicalapplication of functional material such as novel and high-performancelight-emitting elements and electronic parts.

According to the present invention, the superlattice of nanometer-sizedsilicon particles can be produced at a high productivity withoutrequiring a specially expensive device and the like, particles havingsmall variations in particle diameter of the silicon particles formingthe superlattice and small variations in surface level can be arrangedat a remarkable periodicity, so that the material having a desired bandstructure can be produced stably. Thus, the superlattice of the presentinvention can produce various types of band structures in accordancewith the intended use, and when used for functional materials such asnovel light-emitting elements and electronic parts, materialcharacteristics are stabilized, and the performance can be improved withease. Thus, it can contribute to practical application of the functionalmaterials.

1. A silicon particle superlattice comprising a plurality of siliconparticles, wherein the silicon particles have an average particlediameter of 1-50 nm, and a variation coefficient of a particle diameteris 20% or less.
 2. A method for production of a silicon particlesuperlattice, comprising adding a hydrophobic solvent to a suspensionwhich has hydrophobic silicon particles dispersed into water, leavingthe resulting suspension at rest, and arranging the silicon particles atthe interface between an aqueous phase and an organic phase.
 3. Themethod for production of a silicon particle superlattice according toclaim 2, wherein the suspension contains hydrofluoric acid.
 4. Themethod for production of a silicon particle superlattice according toclaim 2, wherein the hydrophobic solvent is 1-octanol.
 5. The method forproduction of a silicon particle superlattice according to claim 3,wherein the hydrophobic solvent is 1-octanol.
 6. A silicon particlesuperlattice structure which has the silicon particle superlatticeaccording to claim 1 on a hydrophobic surface of a solid substrate. 7.The silicon particle superlattice structure according to claim 6,wherein the solid substrate is a silicon substrate or a graphitesubstrate.
 8. A light-emitting element comprising the silicon particlesuperlattice according to claim
 1. 9. An electronic part comprising thesilicon particle superlattice according to claim
 1. 10. A light-emittingelement comprising the silicon particle superlattice structure accordingto claim
 6. 11. An electronic part comprising the silicon particlesuperlattice structure according to claim
 6. 12. A light-emittingelement comprising the silicon particle superlattice structure accordingto claim
 7. 13. An electronic part comprising the silicon particlesuperlattice structure according to claim 7.